ITSAPT seminar, Guimaraes, November 2005 DETERMINATION OF FREE FORMALDEHYDE ON TEXTILE SUBSTRATE BY...

ITSAPT seminar, Guimaraes, November 2005

DETERMINATION OF FREE DETERMINATION OF FREE FORMALDEHYDE ON TEXTILE FORMALDEHYDE ON TEXTILE

SUBSTRATE BY HPLCSUBSTRATE BY HPLC

Bojana VONCINA

University of Maribor, Textile Department

Smetanova 17, 2000 Maribor, Slovenia


Formaldehyde is built in the atmosphere thought photochemical processes of hydrocarbons

It is produced during the uncompleted combustion of wood, oil, gas, tobacco

Source of formaldehyde:

- Automobiles and airplanes 70-80%

- Heating and incineration 13-15%

- Formaldehyde in chem. prod. 1%


Formaldehyde is found in human body as a building blocks for amino acids and proteins

Blood 2-3 mg/kgApple 17-22 mg/kgTomatoes 6-7 mg/kgWood 4-18 mg/kg

Formaldehyde is often used as a building block for a number of important chemical products, intermediates and consumer goods: - urea-formaldehyde resins (25%), - phenol- formaldehyde resins (20%), - plastics (15%), - intermediates (22%).


Toxicity Data

Formaldehyde is readily absorbed through skin and is toxic by

inhalation

It is considered toxic, carcinogen, mutagen, corrosive

Health Effects:

Inhalation: formaldehide is extremely destructive to tissue of the mucous membranes and that of the upper respiratory tract. Inhalation may be fatal as a result of spasm and inflammation.

Eyes/Skin: extremely destructive to the tissue of the eyes and skin. Can cause allergic skin reactions

Ingestion: Can cause gastrointestinal disturbances. May alter genetic material. This is considered a carcinogen.

Target Organs: eyes, kidneys, liver, heart, potential cancer agent, testis, ovaries


The most effective crosslinking reagents for durable press finishing of cellulose fibers are formaldehyde adducts of urea which release formaldehyde during the production and wearing of in such way treated clothes

Formaldehyde durable press finishers are applied to the textile substrate mainly in the form of N-methylol and N-alkoxymethyl compounds

C

O

N CH2OH

CH

OH

CH

OH

NHOH2C

C

O

N CH2

CH

OH

CH

OH

NCH2 O CH3OCH3

DMDHEU modified DMDHEU


Release of formaldehyde from the textile substrate can be measured by:

STANDARD TEST METHODSJapan Law 112 (EN ISO 14184-1)AATCC-112

The formaldehyde content below 20 mg/kg can not be shown to be caused by the formaldehyde which was released by the crosslinking reagent.

ALTERNATIVE TEST METHODS edana recommended test method using HPLCHPLC


EN ISO 14184-1 EN ISO 14184-1 standard test methodstandard test method

Standard solutions of formaldehyde with concentration levels of 0.3, 0.6, 0.9, 3.0, 6.0, 15.0 and 30.0 mg/L in the 3,5, - diacetyl –1,4-dihydrolutidin forms were prepared. The formaldehyde derivative solutions were prepared in water and in matrix (extract from untreated cotton fibers). Six replicates of each concentration level were prepared

From the textile substrateformaldehyde was extracted with water at 40C, filtered and then converted by using acetyl-acetone reagent to yellow colored compound

C

O

CH3

CH2

C

O

CH3

+

C

O

HH

N

H

HH

CH2

C

O

C

O

CH3

CH3C

O

CH3CH2

C

CN

C

C

H

CH3

C

O

CH3

CH3


Validation of absorbance measurements on UV/Vis

With Grubbs and Beck statistical test were shown that there were no aberrant values

An F – test was applied to check heteroscedasticity: standard deviation increase with the concentration

Correlation coefficient for standard water and matrix solutions was greater than 0.99

Quality coefficient (QC) was lower than permitted 5% Anova test shows that the experimental error was smaller than lack of

fit (LOF) for the linear calibration curve Precision of standard water and matrix solutions was better than 10% The limit of detection (LOD) was 0.628 mg/l The limit of quantification (LOQ) was 1.197 mg/l The amount of formaldehyde extracted for each sample can be

calculated by:Konc (x) = 7,493 ABS - 0,06356


Free formaldehyde measured by HPLCFree formaldehyde measured by HPLC • Standard water and matrix solutions of formaldehyde with

concentrations levels 0.075, 0.15, 0.3, 0.6, 0.9, 3.0, 6.0, 15.0 and 30.0 mg/L in the 3,5, - diacetyl –1,4-dihydrolutidin forms were prepared

• Formaldehyde was extracted from textile substrate with water at 40C, filtered and then converted by using acetylacetone reagent to yellow colored compound

HPLC Varian Prostar 210 pump, Varian Prostar 310 UV/Vis detector (at 410 nm), STAR Chromatography Workstation Varian 4.5, LiChrosorb RP-18 coloum with particle size 7 m,


Validation of the HPLC analytical method

The optimisation of the

method (the proper column,

mobile phase, solvents,

temperature of the column

etc.) was done.

The concentration of free

formaldehyde in the aqueous

solution was determined using

peak areas from the standard

and sample chromatograms.

2.25

2.50

2.75 Minutes

0

50

100

150

200

250

300

mAU

Retention time [min]

30 mg/L 15 mg/L 1,5 mg/L 0,3 mg/L

Mobile phase methanol-water (70:30 v/v).

The retantion time for formaldehyde derivative was 2.7 min


Validation of the HPLC analytical method

With Grubbs and Beck statistical test were shown that there were no aberrant values

An F – test was applied to check heteroscedasticity: standard deviation increase with the concentration

Correlation coefficient for standard water and matrix solutions was greater than 0.99

Quality coefficient (QC) was lower than permitted 5% Anova test shows that the experimental error was smaller than

lack of fit (LOF) for the linear calibration curve Precision of standard water and matrix solutions was better than

10% The limit of detection (LOD) was 0.0199 mg/l The limit of quantification (LOQ) was 0.066 mg/l The amount of formaldehyde extracted for each sample can be

calculated by:Konc (x) = 0,2055 * 10-4 AREA – 0,222


CONCLUSIONS

The results obtained by the standard test method, Japan

Law112, were compared with the results obtained by HPLC

method where separation was performed on RP C 18 column

with water-MeOH as a mobile phase.

The limit of detection (LOD) for Japan Law 112 was 0.628 mg/l and the limit of quantification (LOQ) was 1.197 mg/l

The limit of detection (LOD) for HPLC method was 0.0199 mg/l and the limit of quantification (LOQ) was 0.066 mg/l

Matrix has no influence on the formaldehyde content in the analysed solution.


FORMALDEHYDE IN MICROENCAPTULATED TEXTILE MATERIALS

Bojana VONCINA

University of Maribor, Textile Department

Smetanova 17, 2000 Maribor, Slovenia


Introduction

• Essential oils from plants Lavandula sp.(lavender), Rosmarinus sp (rosemary) andSalvia sp. (sage) are natural fungicide andantibacterial agents. • These oils were microencapsuled in melamine-formaldehyde microcapsules and cross linked onPES nonwoven textile materials.• Such textile material is capable ofreleasing formaldehyde by decompositionof microcapsules.


Sources of the formaldehyde

Textile material (PES) cross-linking reagent microcapsules

wall : wall : melamine-formaldehyde resinsmelamine-formaldehyde resins core :core : 25 % 25 % mixture of essential oilsmixture of essential oils, 75 % , 75 % solventsolvent

80 % 80 % mixture of essential oilsmixture of essential oils, 20 % solvent, 20 % solvent mixture of essential oilsmixture of essential oils: - lavender 70 %: - lavender 70 %

- rosemary 20 - rosemary 20 %%

- sage 10 %- sage 10 % solvent: isopropyl solvent: isopropyl mirystatemirystate


Experimental

Release of formaldehyde from the textile substrate was determined by

• EN ISO 14184-1 (Japan Law 112 method),

• AATCC test 112-1998,

• HPLC method, where the separation was achieved with elution using methanol-water, as eluents on a reverse phase column and was monitored at 410 nm with a UV/VIS detector.

In all three methods the extracted

formaldehyde was converted by

using acetylacetone reagent to

yellow coloured compound.


The formaldehyde contents were determined in

different textile samples:

a) untreated textile material (PES nonwoven)

b) textile material with cross-linking reagent (suspension of latex and acrilate emulsifier)

c) textile material with empty microcapsules,

d) textile material with cross-linkinked empty microcapsules,

e) textile material with cross-linked microcapsules filled with oils (25 % mixture of essential oils, 75 % solvent)

f) textile material with cross-linked microcapsules filled with oils (80 % mixture of essential oils, 20 % solvent)

The formaldehyde contents were determine also in mixture of oils and pure rosemary and sage oil.


• Untreated textile material and cross-linking reagent do not contain formaldehyde (7 mg/kg).

• Microcapsule’s walls contribute to the amount of of the

formaldehyde significantly:

•The average formaldehyde content for the microencaptulated

textile material with empty microcapsules is 715 mg/kg and 766

mg/kg for microencaptulated textile material with microcapsules

filled with oils (both results are obtained by Japan Law method).

• Results from AATCC test for the same samples are 5.126

mg/kg and 4.174 mg/kg respectively.

.

Results and conclusions


Results obtained by HPLC method:

• indicate that only formaldehyde is released from the textile samples microencaptulated with and without essential oil.

• Although some amount of formaldehyde is proved in pure essential oils, amount of essential oil which is applied on textile material with microcapsules (160 g/m2) contribute very little to total amount of formaldehyde. This was proved by the measurements of released formaldehyde after the mechanical damages of microcapsules on the textile substrate


Lavender: 0,54 ml/LLavender: 0,54 ml/L Rosemary: 0,15 ml/LRosemary: 0,15 ml/L Sage: 0,32 ml/LSage: 0,32 ml/L

mixture of essential oilsmixture of essential oils : : Average amountsAverage amounts of formaldehyde of formaldehyde: 0,61 ml/L: 0,61 ml/L Results: from 0,18 to 0,75 ml/L (dependent Results: from 0,18 to 0,75 ml/L (dependent

on extraction conditions)on extraction conditions)

FormaldehydeFormaldehyde measurements measurementsin essential oils:in essential oils:


ConclusionConclusion

Results given by AATCC test 112-1978 method are expected Results given by AATCC test 112-1978 method are expected proportionally higher as results given by EN ISO 14184-1 method.proportionally higher as results given by EN ISO 14184-1 method.

The aThe average results verage results obtained from samles prapered in production line obtained from samles prapered in production line are are

lowerlower. T. Those samples hose samples satisfysatisfy eco-labeling system’s requirement. eco-labeling system’s requirement. TThe he explanation for this phenomenon is found in different processes of curing and explanation for this phenomenon is found in different processes of curing and drying. drying.

By HPLC it was proven that there are no other aldehydes or ketones present on microcapsulated textile materiale

IIt was provent was proven that the amount of formaldehyde in essential oils is negligible that the amount of formaldehyde in essential oils is negligible

Microcapsule’s wall contributes to the highest degree of the amount of formaldehyde

After washing of textile substrate, the results are considerable lowerAfter washing of textile substrate, the results are considerable lower

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ITSAPT seminar, Guimaraes, November 2005 DETERMINATION OF FREE FORMALDEHYDE ON TEXTILE SUBSTRATE BY...

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